Sulfated chloroalkanol detergents



SULFATED CHLQRQALELANOL DETERGENTS John C. Cowan, Peoria, 121., and James Knerr Weil,

North Wales, and Alexander James Stir-ton, Philadelphia, Pa., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Original application Sept. 14, 1954, Ser. No. 456,085. Divided and this application Feb. 1, 1957, Ser. No. 640,999

3 Claims. (Cl. 252-161) (Granted under Title 35, US. Code (1952), see. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world, for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the UnitedStates of America.

This application is a division of application bearing Serial No. 456,085, filed September 14, 1954, now abandoned.

This invention relates to processes for producing new and improved detergents and surface-active agents comprising alkali metal salts of sulfated polychloroalkanols.

Sulfated alcohols are valuable detergents and are particularly useful where good foaming properties are required despite the use of hard water. When the higher straight-chain saturated alcohols are sulfated it is observed that detergency and foam-forming power increases as the alkyl group of the alcohol increases from 12 to 18 carbon atoms. However, at the same time, solubility in water decreases in the same order; hence the more efiective compounds are of such low solubility that they cannot be used alone but must be used along with more soluble, but less effective, detergents.

It is known that olefinic double bonds increase the solubility of long-chain compounds. However, such double bonds are chemically reactive and, unless special precautions are taken, will react with the sulfating agent, thus yielding a product having poor detergent properties.

It is also known that chlorine atoms attached to the alkyl group increase solubility, and it has been proposed to prepare detergents from unsaturated alcohols by chlorinating and then sulfating or by simultaneously hydrochlorinating and sulfating such alcohols. When chlorinated alcohols were sulfated by prior art processes, however, some or all of the chlorine was replaced by sulfate groups, thus yielding inferior detergents. When hydrochlorination was used only one atom of chlorine was introduced at each double bond and the beneficial effect was correspondingly small. Use of more highly unsaturated alcohols permitted the introduction of more chlorine but increased the cost of the alcohol correspondingly.

It is an object of this invention to provide 'sulfated polychlorinated, long-chain alkanols that are readily soluble in water and also are highly efiicient detergents and surface active agents. Another object is to provide economical processes whereby high titer animal fats, such as tallow and grease, can be converted and high detergency. Another object is to provide economical processes whereby highly soluble detergents useful for solubilizing and uprading other detergents having only slight solubility may be prepared. Still another object is to provide processes for sulfating chloroalkanols whereby the chlorine is not replaced by sulfate groups. Other objects will appear hereinafter.

According to the invention, fatty alcohol compositions containing at least about 10% of monounsaturated alcohols and not more than about one halfas much poly- States Patent unsaturated. as monounsaturatedalcohols are chlorinated until substantially all double bonds have been saturated with chlorine; then the alcohols. are sulfated at a temperature below that at which the sulfating agent reacts with the chlorine in the alcohols; and finally, the resulting sulfated alkanols are neutralized with an alkali to yield the detergent compounds.

By the expression fatty alcohol composition We mean a composition. consisting essentially of one or more long, straight-chain aliphatic primary alcohols having 10 to 24 carbon atoms, such as, for instance, dodecyl, tetradecyl, hexadecyl, octadecyl, oleyl, linoleyl, elaidyl and similar alcohols and mixtures thereof, and also the mixed fatty alcohols. obtained by the reduction of coconut, palm, cottonseed or partially hydrogenated fish oils, tallow, grease or lard, or the methyl esters derived from such fats and oils. By alkali we mean the oxide, hydroxide or carbonate of an alkali metal.

When the product is to be used directly, that is, without first being blended with other detergents, we may use as starting material a fatty alcohol composition containing as little as about 1 0% of monounsaturated alcohols; where it is to be usedfor blending with other detergents for the purpose of upgrading or solubilizing them, we prefer tostart with fatty alcohols containing at least 40 to 50% of monounsaturated alcohols. In either case a minor amount of polyunsaturated alcohols, up to about one half the amount of monounsaturated alcohols may be tolerated and, in fact, may be desirable, especially when the total unsaturation is relatively low. The preferred raw material for our process is the mixed alcohols obtained from tallow, for instance by sodium reduction, referred to hereinafter as tallow alcohols. Tallow not only has a suitable fatty acid composition but is available in ample quantities at low cost. The commercial inedible greases are likewise especially suitable.

The chlorination of the unsaturated fatty alcohols is carried out as described in the copending application of John Cowan and Howard M. Teeter, filed October 11, 1954, Serial No. 461,691, now abandoned. The alcohol is dissolved in a suitable inert solvent, such as a chlorinated hydrocarbon, and chlorine is passed into the solution while the temperature is maintained below that at which substitution occurs. We prefer a temperature in the range 30 to 10 C. and, better yet, below 0 C. The

chlorine is rapidly and completely absorbed until the alcohol is substantially saturated, at which point absorption of chlorine and evolution of heat substantially cease. The chlorinated fatty alcohol is then recovered in practically quantitative yield by evaporation of the solvent.

The chloroalcohols may be sulfated by use of any suit: able sulfating agent, such as chlorosulfonic acid, sulfuric acid, oleum or sulfur trioxide. The preferred reagent, because of its efliciency and convenience, is chlorosulfonic acid. In order to avoid replacement of chlorine in the alcohol with sulfate groups it is essential to conduct the sulfation at a temperature below that at which replacement occurs. -The temperature should not exceed about 50 C. during the sulfation and preferably should be kept below about 30 C. and may be as low as 0, at least until most of the material has reacted. Since the reaction is strongly exothermic, itis essential that the reagents be mixed slowly with eflicient stirring and cooling. This is facilitated by the use of a suitable inert solvent which may conveniently be the same as was used for the chlorination step. In fact, it is not necessary to recover the chloroalcohol from the, solution obtained in the chlorination step. Instead, after completion of the chlorination the excess chlorine may be removed by aeration, boiling, or otherwise, after which the solution of chloroalcohol is cooled .and sulfated as described above. This is in general the preferred procedure.

. After completion of the sulfation step the reaction mixture is neutralized with an alkali metal hydroxide or carbonate and the resulting salt of the chloroalkyl sulfate is recovered by any suitable means.

Tallow, our preferred raw material, is composed of approximately 16% myristic -acid, 21-35% palmitic acid, 14-30% stearic acid, 36-50% oleic acid and 1-5% polyunsaturated acids. The tallow alcohols obtained by the sodium reduction of tallow contain about the same 7 percentages ofthe corresponding alcohols.

jSeveral experiments were made to illustrate the solubility of the sodium chloroalkyl sulfates and their effect in the solubilization of similar detergents made from saturated fatty alcohols. The solubility of each of 4 compositions was determined by dissolving 0.250 g. of

' the. composition in 100 ml. of hot water, letting the solution stand at 25 C. for several days, and then recovering and weighing the precipitate. The compositions were made up from pure compounds to simulate various products as follows:

Table I shows the composition of each of the 4 tures and the solubility.

TABLE I Comparative Solllbllll) of sulfated fallow alcohols A A B C D from from from from Component, grams oleyl elaidyl oleyl elaidyl alcohol alcohol alcohol alcohol Na tetradeeyl sulfate--- 0. 015 0.015 015 015 015 015 Na hexadecyl sulfate...; 0. 070 0. 070 070 065 .065 065 N a octadecyl sulfate.... 0. 040 0. 040 165 035 O35 035 Ne. oleyl sulfate 0. 125 Na elaidyl sulfa 0. 125 Na 9,10-dlchlorooctadeeyl sulfate (from oleyl alcohol) 135 Ne 9,10-dichlorooetadeeyl sulfate (from elaldyl alcohol) 135 Total weight of components in mixture,

grams 0.250 0.250 .250 .250 .250 115 Insoluble at 25 0., r grsms 0.068 0.052 226 .052 .044. 101 Solubility of mixture at 25 0., grams/100 1111.. 0. 182 0.198 024 198 .206 .014

The results showthat lilse containing either sodium oleyl sulfate, sodium-elaidyl sulfate or sodium 9,10-dichlorooctadecyl sulfates have about the same solusulfated hydrogenated tallow alcohols (B) is onlyabout 0.02%. Solubilization' of the difiicultly'soluble sodium hexadecyl sulfateand sodium octadeeyl sulfateoccurs for mixtures. A and Csince the amount insoluble from C. of less than about 0.2%.

7 The preparation of sodium 9,10-dichlorooctadecyl sulfates, of chlorinated sulfated tallow alcohols, and the measurement of detergent and surface active properties are illustrated in the following examples.

EXAMPLE I Chlorination of octadecanols.-Purified oleyl alcohol, I No. 92.5, estimated purity 97%, was prepared from commercial oleyl alcohol by fractional vacuum distillation and crystallization from acetone at 0 C., -45 C., and -*10 0., following the method of Swern, Knight and Findley (Swern, D., Knight, H. B., and Findley, T. W., Oil & Soap 21, 1339 (1944)). A slow stream of chlorine, gas was introduced into a stirred solution of 100 g. of purified oleyl alcohol in 300 ml. of dichloromethane, cooled in a dry ice-carbon tetrachloride bath maintained at 45" C. Ohlorine was added at such a rate that the reaction temperature remained in the range --l3 C. to 23" C. throughout 4% hours. Completion of the reac, 'tion was indicated by the development of a yellow-green color in the solution and a fall in reaction temperature as a result of no further heat of reaction. Solvent and excess shlorine were removed at reduced pressure. The reaction mixture was finally heated on the steam bath to remove the last trace of solvent and to give a 9,10- dichloroactadecanol as a colorless oil, yield 97%, Ml. 12 C., n 1.4760, d 0.9898, molecular refractivity 96.71 (theoretical value.96.58), I No. 0.3, 19.63% Cl (calculated for C H Cl O, 20.90% C]; calculated with correction for saturated impurities in the oleyl alcohol, 20.46% Cl).

Elaidyl alcohol, I No. 94.7, MJP. 36.1-37.0 C., was prepared as desribecl by Weil, Stirton and Bistline (Weil, I. K.,'Stirton, A. 1., and Bistline, R. G., In, I. Am. Oil Chemists Soc., 31, 000 (1954)), and chlorinated in a similar manner to give 94% yield of a 9,10dichlorooctadecanol as a white solid, M.P. 31 C, n5 1.4757,

7 d5 0.9946, molecular refractivity 96.19,,1 No. 0.3,

- bility at 25 C., namely 0.2%, while the solubility of the mixture D exceeds the amount insoluble from 5 A and C. Sodium 9,10-dichlorooctadecyl sulfates of mixture C, are therefore soluble alone and also solubilize sodium hexadecyl sulfate and sodium octadecyl sulfate,

and are just as efiective' as sodium oleyl sulfate ,and so wherethe solubility is belowlabiout 0.2%. :In such cases,

as litfle as 10% of the polychloroalkyl sulfate detergents 7.14%. s, and 15.87% (:1.

20.59% C1. Sulfa tio n of 9,10-dichlorooctadecyl alcbhoL-Chloro- 'sulfonic acid, 17 g. (0.15 mole), was added dropwise to 'a cold, stirred, solution of 40 g. (0.12 mole) of 9,10-dichlorooctadecanol (from oleyl alcohol, above) in ml. of chloroform, at 6 to 10 C. The reaction mixture was heated to 37 C., maintained at 37 C. for .6 hour, cooled, and neutralizedrwith NaOH,n-butanol, 100 ml., was added and water and chloroform were removed together by distillation. In organic salts were filtered off from the dry, boiling, butanol solution. solution was cooled to 25 C., and filtered to give a 65% yield of a sodium 9,10-dichlorooctadecyl sulfate, :1 light cream colored solid,,purified by treatment with car'- bon and recrystallization, from butanol at 25 C. to give a'39% yield of a sodium 9,10-dichlorooctadecyl sulfate, a white ,solid,.I .No. 0.1, containing 5.01% Na, 7.07% S, and 15.39% Cl (calculated for C H Cl NaO S, 5.21% Na, 7.26 S, 16.06% Cl; 15.72% Cl when corrected for saturated impurities in the oleyl alcohol).

Elaidyl alcohol, chlorinated and sulfated as described above gave 84% yield of a light cream colored solid and 67% yield of a purified sodium 9,10-dichlorooctadecyl sulfate, a white solid, I No. 0.7, containing 5.27% Na,

. r EXAMPLE 11 Chlorinated sulfated allow olcohoIs.'-'A tallow' alcohol,

The butanol.

saponification No. 8.2, acid No. 1.5, I No. 54.1, percent hydroxyl 6.4, was chlorinated and sulfated as described in, Example 1, except that purification steps were omitted. Chlorine was run slowly into a solution of the tallow alcohol in 3 volumes of chloroform at --20 C. until an 5 excess of chlorine was evident. Excess chlorine was expelled by a stream of nitrogen. The iodine absorption of the solution at this point was 0.13 g./ 100 ml. indicating almost complete reaction of chlorine was unsaturated constituents.

Without removal of solvent the chlorinated tallow alcohol was sulfated with 1.09 molar ratio of chlorosulfonic acid at 0 C. to C. Methanol was added and the cold reaction mixture was neutralized with 18 N sodium hydroxide and evaporated to dryness to give a cream colored solid.

The solubility, surface active and detergent properties of this somewhat impure product were in general comparable to mixtures of pure compounds simulating sulfated tallow alcohol and sulfated chlorinated tallow alcohol. The solubility and foaming properties were better than those of a mixture of pure compounds simulating sulfated hydrogenated tallow.

EXAMPLE III Detergent and surface active properties of sodium 9-10- dichlorooctadecyl sulfates-The foaming and detergent properties of sodium 9,10-dichlorooctadecyl sulfates and mixtures containing them are shown in Table 11.

Foam-height was measured by the Ross-Miles test, recorded as the height of foam five minutes after formation (Ross, 1., and Miles, G. D., Oil and Soap 18, 99-l02 (1941)).

Detergency was measured in an experimental Washing machine (Terg-O-Tometer) with standard soiled cotton, initial reflectance relative to MgO as 100, 25.3, using 10 swatches per liter of solution, and washing for 20 minutes at 60 C., at 110 cycles per minute. Detergency was expressed as increase in reflectance, A R, after washmg.

For comparison, values for sodium dodecyl sulfate, sodium oleyl sulfate, sulfated chlorinated tallow alcohol,

7 TABLE 11 ,7 Foaming and detergent properties Foam Height, Detergency, 0.

mm., 60 C. A R Values 0.25% in 0.1% in 0.1% in 025% in distilled water water water water of 100 of 100 of 300 p.p.m. p.p.m. p.p.m.

hardness hardness hardness Sodium dodecyl sulfate 175 248 24. 8 24. 5

Sodium oleyl sulfate 240 226 34. 8 24. 0 Sodium 9,10-dichlorooctadecyl sulfate (from oleyl alcohol) 235 205 31. 5 22. 2 Sodium 9,10-dichlorooctadecyl sulfate (from elaidyl alcohol 245 209 32. 8 21. 7 sulfated chlorinated tallow alcohol (of Example II,

without purification) 238 208 29. 5 22. 9 Mixture A. sulfated tallow alcohol M9 216 30. 7 26. 1 Mixture B. sulfated hydrogenated tallow alcohol. 244 72 36.8 34. 4 Mixture O. sulfated chlorinated tallow alcohol 243 208 34. 8 24. 5

In Table HI the calcium stability, surface and interfacial tension, and wetting properties of the sodium 9,10- dichlorooctadecyl sulfates are compared with those for sodium dodecyl sulfate and sodium oleyl sulfate.

Calcium stability was measured by a modified Hart method (Wilkes, B. G., and Wickert, J. N., Ind. Eng. Chem. 29, 1234-9 (1937)).

Wetting properties are recorded as the sinking time for a standardized binding tape by the method of Shapiro (Shapiro, L., Am. Dyestuff Reptr. 39, 38-45, 62 (1950)).

The sodium 9,10-dichlorooctadecyl sulfates have calcium stability values intermediate between those for sodium dodecyl sulfate and sodium oleyl sulfate. Surface and interfacial tension values are about the same as those for sodium oleyl sulfate. Wetting properties measured by sinking time show that the sodium 9,10-dichlorooctadecyl sulfates are quite stable to hydrolysis in boiling 1% sodium hydroxide, but like the other alcohol sulfates they are hydrolyzed in hot 5% sulfuric acid solution.

TABLE 111 Surface active properties Surface and Intertaclal Sinking Time, 0.1% Concn. of Tension, 0.1% Surface Active Agent, 25 0., Solns., dynes/ Seconds Boiled 1?; Stabilcm. 25 0. g p.p.m.

0500. Hist?) Boiled S.T. LT. Distd. 1% 4 Hrs 5% Water NaOH in 1% H1804 aOH N a dodecyl sulfate 550 49. 0 20. 3 13 13 17 15 600 Na oleyl sulfate 1, 800 35.0 7. 4 19 23 31 3O 600 Na 9,10-dichlorooctadecyl sulfate (from oleyl alcohol) 970 35. 8 5. 8 32 53 46 62 600 Na 9,10-dichlorooctadecyl sulfate (from elaidyl alcohol) 950 35. 8 6. 0 39 66 57 70 600 and mixtures of pure compounds simulating the composi- We claim:

tion of sulfated tallow alcohol (A), sulfated hydrogenated tallow alcohol (B), and sulfated chlorinated tallow alcohol (C), are included. Mixtures A, B and C have the same composition as those similarly designated in Table I.

1. A detergent composition comprising an anionic detergent having a solubility in water at 25 C. of less than about .2% and having the general formula CH3 HCH OSOgM From Table II it is apparent that sodium oleyl sulfate 70 wherein n is an integer selected from the group consistand sodium 9,10-dichlorooctadecyl sulfates have similar solubility, foaming, detergent, and surface active properties. Sulfated chlorinated tallow alcohol has much better solubility than sulfated hydrogenated tallow alcohol, and better foaming properties in hard water.

ing of numerals 14 and 16 and M is an alkali metal, and as a solubilizing agent therefor, about from 10% to 50% of sodium 9,10-dichlorooctadecyl sulfate.

2. The detergent composition of claim 1 wherein the anionic detergent is sodium hexadecyl sulfate.

3. The detergent compdsitibli 'af claim 1 wherein the anionic detergent is sodium octadecyl sulfate.

M Q] FoRElsNgrATENfrs V 7 V H w 7 400,986: Greet Britain Nov. 6 1933 References Cited in the file of this patent i 9 n O fi ik iE UNITED STATES PATENTS 5 r Mai-tin: "fThe' Modern Soap and Detefgent lhdlistry,

2,139,669 Buc Dec. 13, 1938 1931, Londp'mvol. 1', sec. 1, pages 7 and 10. 2 ,462,758 Malkemus Feb. 22, 1949 7 

1. A DETERGENT COMPOSITION AN ANIONIC DETERGENT HAVING A SOLUBILITY IN WATER AT 25*C. OF LESS THAN ABOUT .2% AND HAVING THE GENERAL FORMULA 